Method of processing phosphorus sludge



v simple manner without,isolatiosttgmths Sludsezar'ldf-this contrary 4to-the known processes'wherein the'llnhosphorusy ihstobe.isolated-,in a verysdisadyantageous manne lphorus sludge to be dispensed with.

. 'may be mixed with pure, yellow` phosphorus `,and then for aanpassingiiirosgndnusistnnea Ttiisinventio relate ed hyevapor y o H reduced pressure at a temperature immediately #below L' `nt s? latter case,

rthefaffsfrstso obtainedg-xfn'ay Vbehydi'at'edf wit cfu/aten to 'form a phdsphoricmaid Y A,

luted to a desired concentration by the addition of a further quantity ofwater." v ,n o l "l The process herein described enables the phosphorus lcontained ina'phosphoius` Sludge ftolfbe'V utilized in m65 nd the 121108-,

furthermore enables a separatepreparation of As a general principle,` any type vof a phosphorus sludge tainsV between' about y2.5 and; about .75 of phosphorus affich,accrdingly,'.between about-2.5% andabout 7.5% vof water, linladdition'to about to about 4%1' of solidin1- phorus'sludge whichfco'ntains betweenv about 40%'and about 60% of phosphorus and,y accordingly, between about 40% `andabout160371?of water iiraddition to about 2%'fisolidimpurities*` ,A

"1 Theupper .limit of "v hef'lpr'occsrsable sludgeportion-'iii "the `mixture of' phosphorus sludge and phosphorusjis aboutv 50%. It must, howeverg'befnotedthat the' consistency 'of the phosphorus sludgeV '.mjay jvary *within wide -limits depending onfthe nature r"of Y,the crudej .phosphateA used. Hence; it is'possible'thatinthec'aseof some, phosphates the f use lof, a homogeneous. mixture of 50% oizjplire .yel-

low. phosphorus "and`f}50.%' 4 of .phosphorusA sludge"A is' fno v longer kassociatedjwithasrnooth burning operation. y'lhe v endmixturefmustyhowever, f be'able at a corresponding 1 temperature of 4being pumped and burned like pure,1ye1

'lowf phosphorus'to forth phosphorus pentoxide. As foli flows, the'upperflimitof 5 0'%"of the phosphorus sludge y proportion'varies ,depen'dixligV onfthe consistency of. the

sludge'. Generally, o the mixing proportion of v phosphorus sludge to'pure phosp bly `washed out with' vwater lwhile', avoiding .an additional adsorption of'water andjmt'hispriortobeing mixed with the pure,

lliqnidfjand'yellowphosphorus. .During this operation, ywhich/is carried outp'rio'r'v to the .homogenization,v no

additional; water absorbed by` the sludge,. since the specific gravities. off'thethr'ee liquidllayers, i.e.`phos phorus; z:phosphorus ,sludge'andxwaten differ very much from oneanothenf y o' l' Thev aqueous' phosphorus sludge; is then'omixed with the 'purefyellow phosphorus atia` tei'riperature abovethe meltingpo'int' o't yellow phosphorus, preferably at a temi peraturebetvve'en vabout '-80..C.:-1and aboutg`90 C. This ylatter -temperature of 90 C. displays an especially favorable effectin rpreparing thejiabove mixture since the viscosity 'of 'liquid phosphorus decreases` with an'increas- Y ing temperature.

' Yellow phpgfpnqrusisstsred in the: iiqiiid farm together lwith vtljressludgein' heated` storage tanks which are lkept at a'constant temperature means-gotha heating'ja'clet.

f In these tanks', thepure, yellowphosphorus or the :mix-

" ture of phosphorus'l and phosphorus sludge is covered with f a water layer tozprevent the access of air." To obtain a homogeneous'pmass-of phosphorus and phosphorus sludge,

mixing is performed according to" this inventionbyfs'tir- 'ring or injectingijan inertf'gasinto the phosphorus .and phosphorus sludgeflayers- The two layers of phosphorus l i and phosphorus sludgemayfbestirred.only so intensively 'that, while avoiding ak turbulent flow, both layers are intimately mixed Vwith .oneganotherg .but .remain'unmixed with Athe coveringf'waterfrlayer. 4This lmay be achieved during k .thea .mixing iop'er'ationwby using a slowly operating lblade u stiurrei.'l Such stirrer enables the 'phosphorus` sludgewhich v-iloatsfouffthe4 phosphorus melt to be intimately'mixe'dwith theryellow'phosphorus"iwithf formation of a homogeneous 'dispersion of the 's1u'dge:in-1the1i`quid phosphorus;` i

2 *When fthe'i 'homogeneous mixture obtained.y isf allow'ed to instand for. solme'hours;` the sludge separates againfiasj an individual ...layer abovefthe phosphorus Sand hasf'rn'owffap` ther-:other'lhandgiitkqis ladvisable*that' Lthez'faqueous: phosphorussludge mixed with the pure, yellowlphos'phrusbe burned to form phosphorusI pentoxide whilek constantly Y 70 maintaining the homogeneity of the mixture.k The sludge v `disperses iinely in 'the phosphorus so that thejvvater ad- .n hering to said sludge is also introduced into the furnace, f

i. infisso e A 'orusisl within the range of' about 1:1 andabout 1:10, and preferably` about 1:5.

The aqueous phosphorusk sludge is advis It should also be noted that the mixture must be kept in a fairly homogeneous state during *the entire burning operation.

The ,homogeneous mixtureof aqueous phosphorus sludge and pure phosphorus that is to undergo a burning process should advisably be introduced into the furnace at a temperature of between about 80 C. and about 90 C.'and burned at that temperature to form phosphorus pentoxide.` Pure yellow phosphorus alone is normally burned at a temperature as'indicated above so that the burning conditions are identical. l

As follows, the temperature applied during the mixing i operation is maintained during the loading operation and the burning process itself.y It is understood that pure yellow phosphorus or a mixture of phosphorus and phosphorus sludge is more dilcult to burn at a temperature lower than'indicated above since the viscosity of both substances is higher at such lower temperature. Contrary thereto, the application of a lower temperature does not involve a separation of the mixture into phosphorus sludge and phosphorus so that the pumpability of the whole mixture is warranted even at such a lower temperature.

The mixture is burned to form phosphorus pentoxide, then hydrated and optionally diluted with water to form an acid. This acid contains small amounts of solids whichderive from the sludge and can be separated in any desired manner, for example by iltration. In this respect it must be stressed that a phosphoric acid produced according to this invention from a mixture of yellow phosphorus and a phosphorus sludge which has'previ ously been washed out, does not differqualitatively from a phosphoric acid producedfrom pure phosphorus.

The process of this. invention offers the particular advantage that for processing the sludge it need not be isolated, for example by skimming, for the sludge stored in a heatable tank is not removed, but is burned together with pure phosphorus and, like this latter substance itself, without necessitating additional apparatus to be used.

The following examples serve to illustrate' the invention, but they are not intended to limit it thereto:

Example 1 l5 tons of yellow phosphorus containing 99.9% of phosphorus are stirred for 6 hours at a temperature of about 80 C. to 90 C. with 15 tons of a phosphorus sludge which contains, for example, about 40% to 60% of phosphorus, about 2% to 4% of solid impurities and about 40% to about 60% of water, with formation of a homogeneous mixture. The mixture so obtained is then burned in known manner ata temperature above the melting point of phosphorus, preferably at 80 C. to 90 C., tol form phosphorus pentoxide which is then hydrated with the necessary amount of water to obtain a phosphoric acid which is then diluted to a desired concentration by the addition of a further quantity of water.

Example 2 30 tons of pure yellow phosphorus containing 99.9% of phosphorus are stirred for 4 hours at a temperature of 80 C. to 90 C. with 6-tons of a sludge containing, for example, 40% of phosphorus, about 2% of solid impurities and about 60% of water, with formation of a homogeneous mixture. Like pure yellow phosphorus, the mixture so obtained is then burned in known manner at a temperature above the melting point of phosphorus, preferably at 80 C. to 90 C. to form phosphorus pentoxide which is then hydrated with the necessary quantity l of water to obtain a phosphoric acid which is diluted to a desired yconcentration by the addition of a further quantity of water.

i Example 20 tons of yellow pure phosphorus containing 99.9% of phosphorus are stirred for 2 hours at a temperature of 80 C. to 90 C. with 2 tons of a sludge which contains, for example, 25% of phosphorus, up to about 4% of solid impurities and between about 70% and 75% of water, with formation of a homogeneous mixture. Like pure yellow phosphorus, the mixture so obtained is burned in known manner `at a temperature above the melting point of phosphorus, preferably of 80 C. to 90 to form phosphorus pentoxide which is then hydrated with the necessary quantity of water to give a phosphoric acid which can be1diluted Yto a desired concentration by the addition of a further quantity of water.

We claim:

1. The method of converting to phosphorous pentoxide the phosphorous contained lin the stiti aqueous phosphorus sludge layer obtained in the thermal reduction of phosphorus, containing orc which comprises thermallyreducing phosphorus containg ore and thereby obtaining a phosphorus vapor stream; condensing said phosphorus vaporstream by spraying with water in the absence of oxidizing conditions; collecting resulting condensate vand allowing it to separate as an intimate three phase system comprising a lower layer of `substantially pure yellow liquelied elemental phosphorus, an intermediate phosphorus sludge layer which is an aqueous dispersion of elemental phosphorus and solid impurities and an upper protective water layer; homogeneously mixing said phosphorus sludge layer containing from Vabout 25 to 75% by .weight of elemental phosphorus, from about to 25% by weight of water and from about 2 to 4% by weight of solid impuritieswith at least an equal weight of the substantially pure, vyellow liquefied elemen- Vtal phosphorus of the lower layer of the same condensate; oxidizing .the phosphorus content of said homogeneous mixture to`phosphorus pentoxide at a temperature of about lto 90 C., and maintaining the mixturein its homogeneous condition during the oxidation step.

2. The process of claim 1 wherein the proportion by weightA of substantially pure yellow liquefied elemental phophorus admixed `with the intermediate phosphorus sludge layer of the same condensate is between about 1:1 to about 10:1.

3. The process of claim 1 wherein the intermediate phosphorus .sludge layer is washed with water without substantially affecting the nal water content thereof and prior to hornogcneously mixing with the substantially pure yellow liquefied elemental phosphorus of the same condensate. t

4. The process of .claim 1 wherein the, intermediate phosphorus sludge ,layer and the substantially pure yellow liqueed elemental phosphorus of the same condensate are homogenized by bubbling a nonreactive gas through said layers while avoiding disturbance of the protective aqueous layer covering the mixture.

5. The process of. claim 1 wherein the .intermediate phosphorussludge layer contains about 40 to 60% by weight of phosphorus, 60 to 40% by weight of water and about 2 to `4% by weight of solid impurities, and wherein the` substantially pure yellow liquefied elemental phosphorus of the same condensate is mixed with said vintermediate.phosphorus sludge'layer in a ratio of' about References Cited in the file of this patent l UNITEDSTATES PATENTS y 51,990,233 nechenbieikner Feb. 5, 1935 2,020,916 Uay Nov. 12,1935 Annoner Nov. 19, 1940 

1. THE METHOD OF CONVERTING TO PHOSPHOROUS PENTOXIDE THE PHOSPHOROUS CONTAINED IN THE STIFF AQUEOUS PHOSPHORUS SLUDGE LAYER OBTAINED IN THE THERMAL REDUCTION OF PHOSPHORUS CONTAINING ORE WHICH COMPRISES THERMALLY REDUCING PHOSPHORUS CONTAING ORE AND THEREBY OBTAINING A PHOSPHORUS VAPOR STEAM, CONDENSING SAID PHOSPHORUS VAPOR STEAM BY SPRAYING WITH WATER IN THE ABSENCE OF OXIDIZING CONDITIONS, COLLECTING RESULTING CONDENSATE AND ALLOWING IT TO SEPARATE AS AN INTIMATE THREE PHASE SYSTEM COMPRISING A LOWER LAYER OF SUBSTANTIALLY PURE YELLOW LIQUEFIED ELEMENTAL PHOSPHORUS, AN INTERMEDIATE PHOSPHORUS SLUDGE LAYER WHICH IS AN AQUEOUS DISPERSION OF ELEMENTAL PHOSPHORUS AND SOLID IMPURITIES AND AN UPPER PROTECTIVE WATER LAYER, HOMOGENEOUSLY MIXING SAID PHOSPHORUS SLUDGE LAYER CONTAINING FROM ABOUT 25 TO 75% BY WEIGHT OF ELEMENTAL PHOSPHORUS, FROM ABOUT 75 TO 25% BY WEIGHT OF WATER AND FROM ABOUT 2 TO 4% BY WEIGHT OF SOLID IMPURITIES WITH AT LEAST AN EQUAL WEIGHT OF THE SUBSTANTIALLY PURE, YELLOW LIQUEFIED ELEMENTAL PHOSPHORUS OF THE LOWER LAYER OF THE SAME CONDENSATE, OXIDIZING THE PHOSPHORUS CONTENT OF SAID HOMOGENEOUS MIXTURE TO PHOSPHORUS PENTOXIDE AT A TEMPERATURE OF ABOUT 80 TO 90*C., AND MAINTAINING THE MIXTURE IN ITS HOMOGENEOUS CONDITION DURING THE OXIDATION STEP. 